Global ab Initio Potential Energy Surface for the O₂(³Σ_g ^–) + N₂(¹Σ_g ⁺) Interaction. Applications to the Collisional, Spectroscopic, and Thermodynamic Properties of the Complex

Abstract

A detailed characterization of the interaction between the most abundant molecules in air is important for the understanding of a variety of phenomena in atmospherical science. A completely ab initio global potential energy surface (PES) for the O2((3)Σg(–)) + N2((1)Σg(+)) interaction is reported for the first time. It has been obtained with the symmetry-adapted perturbation theory utilizing a density functional description of monomers [SAPT(DFT)] extended to treat the interaction involving high-spin open-shell complexes. The computed interaction energies of the complex are in a good agreement with those obtained by using the spin-restricted coupled cluster methodology with singles, doubles, and noniterative triple excitations [RCCSD(T)]. A spherical harmonics expansion of the interaction potential containing a large number of terms due to the anisotropy of the interaction has been built from the ab initio data. The expansion coefficients, which are functions of the intermolecular distance, are matched in the long-range with the analytical functions based on the recent ab initio calculations of the electric properties of the monomers [M. Bartolomei et al. J. Comput. Chem. 2011, 32, 279]. The PES is tested against the second virial coefficient B(T) data and the integral cross sections measured with rotationally hot effusive beams, leading in both cases to a very good agreement. The lowest lying states of the complex have been computed and relevant spectroscopic features of the interacting complex are reported. A comparison with a previous experimentally derived PES is also provided.

Recent developments in symmetry‐adapted perturbation theory

“…For the oxygen dimer example mentioned above, SAPT(ROHF)/SAPT(UHF)/… are capable of describing the interaction in the quintet state, which happened to be one of the first applications of SAPT(ROKS) . Another atmospherically relevant interaction is the O 2 –N 2 one, for which a ground‐state PES was constructed using SAPT(DFT) and used to accurately reproduce experimental second virial coefficient data and integral cross sections. Several interactions involving nitrogen oxides, important atmospheric pollutants, have also been thoroughly investigated using open‐shell SAPT and/or SAPT(DFT): NO–H 2 O and NO 2 –H 2 O .…”

Kinetic Models of Oxygen Thermochemistry Based on Quasi-Classical Trajectory Analysis

“…This PES was designed specifically for methods of molecular dynamics for the upper atmosphere, however, it has a little use for aerothermodynamics. Bartolomei et al [70] recently published an improved ab-initio PES with similar restrictions. The VT and VV energy transfer was studied by a semiclassical coupled method by Billing on an empirical PES in the range of temperatures between 250 and 1000 K [26].…”

State-resolved O2--N2 kinetic model at hypersonic temperatures

“…This PES was designed specifically for methods of molecular dynamics for the upper atmosphere, however it has a little use for aerothermodynamics. Bartolomei et al [36] recently published an improved ab-initio PES with similar restrictions. The vibration-translation (VT) and vibration-vibration (VV) energy transfer was studied by a semi-classical coupled method by Billing on an empirical PES in the range of temperatures between 250 and 1000 K [23].…”